Method for preparing photoluminescence transparent glass through photocuring 3D printing

Abstract

The invention discloses a method suitable for VPP photocuring 3D printing photoluminescent glass, and relates to a slurry formula, a manufacturing process and a Ce ion doping method. The slurry is composed of a plurality of organic matters with specific contents and silicon oxide powder. And carrying out three times of heat treatment under different conditions and at different temperatures, and carrying out Ce ion doping treatment. According to the invention, the problems of insufficient precision and low efficiency when the photoluminescent glass with a complex fine structure is prepared by a traditional method are solved, the forming precision and performance of the photoluminescent glass are greatly improved, and the preparation period is shortened; by optimizing a slurry formula and a photocuring 3D printing process, the structural uniformity and interlayer binding force of the photoluminescent glass are remarkably enhanced, and by researching a heat treatment and doping process, the overall strength and durability are improved; and the comprehensive technical effect is excellent.

Description

Technical Field

[0001] The present invention relates to the technical field of VPP photocuring 3D printing ceramic technology scheme design and application, and particularly relates to a method for preparing photoluminescent transparent glass by photocuring 3D printing. Background Art

[0002] Photoluminescent glass is a functional material with excellent optical and mechanical properties, and is widely used in the fields of optical devices, display technology, sensors, and high-end decorative materials. The traditional preparation methods of photoluminescent glass usually rely on mold forming or melting processing. Affected by the process complexity and mold limitations, it is difficult to prepare complex and delicate structures, and there are also problems such as low forming accuracy, long cycle, and low efficiency. In recent years, the introduction of 3D printing technology has provided a new solution for the preparation of photoluminescent glass. Among them, the voxel projection lithography (VPP) method based on photocuring technology has attracted much attention due to its high precision and high efficiency. The basic principle of VPP photocuring 3D printing of photoluminescent glass is to use a slurry containing a photosensitive resin and functional glass powder to rapidly form a green body under selective irradiation of a light source, and then prepare the photoluminescent glass through debinding and sintering. Therefore, the present invention combines 3D printing technology with photoluminescent glass, and realizes high-precision and high-efficiency preparation through a suitable slurry formula, precise heat treatment temperature control, and innovative doping methods, while improving the mechanical and optical properties of photoluminescent glass to meet the needs of high-end applications. Summary of the Invention

[0003] To solve the above technical problems, the present invention provides a method for VPP photocuring 3D printing of photoluminescent glass, which realizes a high-precision and high-efficiency preparation process by optimizing the slurry formula, precisely controlling the heat treatment temperature, and adopting a unique doping process, while significantly improving the mechanical and optical properties of photoluminescent glass to meet the needs of high-end applications.

[0004] The technical solution adopted by the present invention is: a method for VPP photocuring 3D printing of photoluminescent glass, which includes the following steps:

[0005] Step 1, preparation of glass photocuring printing slurry and green body

[0006] Add the photosensitive resin, solvent, photoinitiator, photoabsorbent and other additives into a mixer in proportion and mix evenly, then add the silicon oxide ceramic powder into the photosensitive resin slurry in batches and through multiple homogenization treatments, and prepare the glass ceramic printing slurry. Add the prepared slurry into a photocuring 3D printing device and directly form it through photocuring 3D printing technology to obtain a glass green body;

[0007] Step 2, debinding treatment

[0008] Put the green body obtained in Step 1 into an atmosphere furnace for high-temperature debinding treatment according to the characteristics of the resin slurry. After completion, introduce air and raise the temperature again for decarbonization treatment.

[0009] Step 3, doping and modification treatment

[0010] Put the sample after decarbonization in Step 2 into a modification solution for modification doping;

[0011] Step 4, sintering treatment

[0012] Put the sample after doping and modification in Step 3 into a vacuum furnace for sintering treatment to obtain a photoluminescent transparent glass sample.

[0013] The method for VPP photocuring 3D printing of photoluminescent glass according to the present invention preferably claims the following technical content:

[0014] In the preparation of the glass photocuring printing slurry and the green body in Step 1.

[0015] One of the photosensitive resin monomers mentioned is composed of one or more mixtures of 2-hydroxyethyl methacrylate, tetramethylol ethylene diacrylate, and 1,6-hexanediol dimethacrylate;

[0016] Two of the solvents are composed of one or more mixtures of polyethylene oxide, polyethylene glycol, and polyvinylpyrrolidone. The total content ratio of these two components in the photocuring printing slurry is 35wt% - 55wt%.

[0017] Three of the photoinitiators are one or more mixtures of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and camphorquinone, and their content accounts for 1wt% - 5wt% of the photosensitive resin component.

[0018] Four of the light absorbers are one or more mixtures of Sudan Orange, p-xylene glycol, and styrene, and their content accounts for 0.01wt% - 1wt% of the overall glass slurry.

[0019] Further preferably: In Step 1, the particle size of the silicon oxide ceramic powder is 50nm - 2um, accounting for 40wt% - 80wt% of the overall photocuring slurry.

[0020] In the debinding treatment of the printed green body in Step 2, the two-step debinding process parameters are: First, under an argon atmosphere, raise the temperature from room temperature to 600°C - 800°C at a heating rate of 0.1°C / min - 2°C / min, and keep it warm for 2 hours, then cool to room temperature; Subsequently, introduce air for decarbonization treatment, raise the temperature from room temperature to 300°C - 500°C at a heating rate of 0.1°C / min - 2°C / min, and keep it warm for 2 hours, then cool to room temperature, and finally obtain the decarbonized sample.

[0021] In the doping modification treatment described in Step 3, the doping modification solution is an ethanol solution prepared from one or more metal nitrates such as cerium nitrate, strontium nitrate, and aluminum nitrate, and the metal nitrates account for 0.1 wt% - 20 wt% of the overall solution. The modification method is to place the decarbonized sample in the modification solution, soak it under vacuum conditions for 1 h - 2 h, then transfer the sample to a drying oven and dry it at 60°C - 80°C for 1 - 2 h to finally obtain the modified sample.

[0022] The sintering process described in Step 4 is to place the sample in a vacuum furnace with a pressure of 0 atm - 0.1 atm, raise the temperature from room temperature to 1200°C - 1400°C at a heating rate of 0.5°C - 2°C / min, hold for 2 hours, and then cool to room temperature to finally obtain the photoluminescent transparent glass.

[0023] Compared with the prior art, in the process of preparing the slurry of the present invention, the photosensitive resin and photoinitiator provide the ability of photocuring, the solvent provides the ability to mix fully with the silica powder and prevent shrinkage and warping during the photocuring process, and the light absorber provides the ability to prevent scattering during the photocuring process, improving the printing accuracy. Each component cooperates with each other to improve the mechanical properties and accuracy of the printed green body.

[0024] In the debinding process, first in argon, the debinding is mainly thermal decomposition rather than combustion, generating less and more controllable gas volume, which can effectively reduce the stress concentration inside the green body, and then air is introduced for low-temperature oxidation treatment to remove the residual carbon element. The two-step debinding method can reduce the risk of cracks and defects and improve the structural uniformity of the glass green body.

[0025] During the doping process, when the decarbonized glass green body is immersed in the ethanol solution of cerium nitrate, cerium ions diffuse into the surface and interior of the glass green body through the solution. During the high-temperature sintering process, cerium ions chemically react with the glass matrix to form stable luminescent centers. When irradiated with ultraviolet light or other excitation light sources, cerium ions can absorb light energy, and electrons transition from the ground state to the excited state. Subsequently, when the electrons return from the excited state to the ground state, they will release energy and emit it in the form of light, which is the phenomenon of photoluminescence.

[0026] The sintering process is carried out in a vacuum, and the gas content is greatly reduced, reducing the hindrance effect of gas between particles, making it easier for particles to contact and move, increasing the diffusion rate of atoms and ions inside the glass, promoting the combination between particles, thus enhancing the densification speed, and improving the density, light transmittance, and mechanical strength of the glass.

[0027] The photoluminescent glass prepared by the method of VPP photocuring 3D printing of photoluminescent glass of the present invention has no delamination phenomenon, good mechanical properties, excellent transparency, and a light transmittance of 80%-90%. Its comprehensive technical effect is excellent. Description of the Drawings

[0028] Figure 1 It is a sintered sample without Ce ion doping under natural light (left) and a sintered sample with Ce ion doping under natural light (right).

[0029] Figure 2 It is a sintered sample without Ce ion doping under ultraviolet light (left) and a sintered sample with Ce ion doping under ultraviolet light (right). Detailed Embodiments

[0030] The present invention will be described in detail below in conjunction with specific embodiments. The description in this part is only exemplary and explanatory, and should not have any restrictive effect on the protection scope of the present invention.

[0031] Example 1

[0032] A method for VPP photocuring 3D printing of photoluminescent glass

[0033] Step 1, preparation of photocurable glass slurry and printed blank;

[0034] 2-Hydroxyethyl methacrylate, 1,6-hexanediol dimethacrylate, and polyethylene oxide were mixed in a mass ratio of 5:4:1 to obtain a slurry resin base, which was put into a blender for mixing. At the same time, 50 wt% of 200 nm silica powder was added in small amounts and multiple times. After mixing evenly, 1 wt% of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide in the photosensitive resin was added, and 0.1 wt% of Sudan orange in the overall photocurable slurry was finally added. Then it was put into a homogenizer and vacuum homogenized at 2000 rad / min for 120 s to obtain the photocurable glass slurry. Then it was put into a photocuring device for printing to obtain a blank.

[0035] Step 2, debinding treatment;

[0036] The printed blank was put into a tube furnace and argon was introduced. It was heated from room temperature to 300 °C at a rate of 1 °C / min, held for 1 h, then heated to 600 °C at a rate of 0.8 °C / min and held for 2 h, and finally cooled to room temperature. Then air was introduced, and it was heated from room temperature to 500 °C at a rate of 1 °C / min and held for two hours, and then cooled to room temperature to obtain the debound sample.

[0037] Step 3, doping treatment;

[0038] Prepare an ethanol solution containing 5 wt% cerium nitrate and 2 wt% strontium nitrate. Place the degreased sample in the solution and soak it for 1 h under vacuum conditions. Then transfer the sample to an oven and dry it at 80 °C for 2 h to finally obtain the modified sample.

[0039] Step 4, sintering treatment;

[0040] Place the modified sample in a vacuum furnace with a pressure of 0.001 atm. Heat it from room temperature to 1200 °C at a heating rate of 1 °C / min and hold for 2 h, then cool it to room temperature to finally obtain the photoluminescent transparent glass. The prepared photoluminescent glass has a light transmittance of 79% and a photoluminescence efficiency of 85%.

[0041] Example 2

[0042] Step 1, preparation of photocurable glass paste and printed blank;

[0043] Mix 2-hydroxyethyl methacrylate, tetramethylol ethylene diacid ester, polyethylene oxide, and polyethylene glycol in a mass ratio of 5:4:1:1 to obtain a paste resin matrix. Put it into a blender for mixing. At the same time, add 60 wt% of 100 nm silica powder in small amounts and multiple times. After mixing evenly, add 1 wt% of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide of the photosensitive resin, and add 0.1 wt% of p-xylene glycol to the whole photocurable paste. Finally, put it into a homogenizer and perform vacuum homogenization treatment at 2000 rad / min for 120 s to obtain the photocurable glass paste. Then put it into a photocuring device for printing to obtain a blank.

[0044] Step 2, debinding treatment;

[0045] Put the printed blank into a tubular furnace and introduce argon. Heat it from room temperature to 260 °C at a rate of 0.5 °C / min, hold for 1 h, then heat it to 600 °C at a rate of 0.5 °C / min and hold for 2 h, and finally cool it to room temperature. Then introduce air and heat it from room temperature to 450 °C at a rate of 0.5 °C / min, hold for two hours, and then cool it to room temperature to obtain the degreased sample.

[0046] Step 3, doping treatment;

[0047] Prepare an ethanol solution containing 4 wt% cerium nitrate and 2 wt% aluminum nitrate. Place the degreased sample in the solution and soak it for 2 h under vacuum conditions. Then take out the sample and transfer it to an oven and dry it at 75 °C for 2 h to finally obtain the modified sample.

[0048] Step 4, sintering treatment;

[0049] The modified sample was placed in a vacuum furnace with a pressure of 0.01 atm, heated from room temperature to 1200 °C at a heating rate of 1 °C / min, held for 3 hours, then cooled to room temperature, and finally a photoluminescent transparent glass was obtained. The prepared photoluminescent glass had a light transmittance of 81% and a photoluminescent efficiency of 88%.

Claims

1. A method for preparing photoluminescent transparent glass by photocuring 3D printing, characterized in that: The following steps are involved: Step 1, preparation of glass photocuring printing slurry and blank; The photosensitive resin, solvent, photoinitiator, light absorber and other additives are mixed in a mixer and stirred evenly, and then the silicon oxide ceramic powder is added to the photosensitive resin slurry in batches, and the slurry is homogenized multiple times to obtain a glass ceramic printing slurry; the slurry is placed in a photocuring 3D printing device, and a glass blank is directly formed by a photocuring 3D printing method; Step 2, degreasing treatment; The green body obtained in step 1 is placed in an atmosphere furnace for high-temperature degreasing treatment according to the characteristics of the resin slurry, and after completion, air is introduced and the temperature is raised again for decarburization treatment; Step 3, doping modification treatment; The sample after decarburization in step 2 is placed in a modification solution for modification and doping; Step 4, sintering treatment; The sample after doping and modification in step 3 is placed in a vacuum furnace for sintering to obtain a photoluminescent transparent glass sample.

2. The method for preparing photoluminescent transparent glass by photocuring 3D printing according to claim 1, characterized in that: The photosensitive resin monomer described in step 1 is a mixture of one or more of 2-hydroxyethyl methacrylate, tetrahydroxymethyl vinyl diacid, and 1,6-hexanediol dimethacrylate, and the solvent is a mixture of one or more of polyoxyethylene, polyethylene glycol, and polyvinyl pyrrolidone, and the above two components account for 35wt%-55wt% of the overall photocurable printing slurry.

3. The method for preparing photoluminescent transparent glass by photocuring 3D printing according to claim 1, characterized in that: The photoinitiator in step 1 is a mixture of one or more of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and camphorquinone, accounting for 1wt%-5wt% of the photosensitive resin component; the light absorber is a mixture of one or more of Sudan orange, p-terephthalic acid, and styrene, accounting for 0.01wt%-1wt% of the overall glass slurry.

4. The method for preparing photoluminescent transparent glass by photocuring 3D printing according to claim 1, characterized in that: In step 1, the silicon oxide ceramic powder has a particle size of 50nm-2um and accounts for 40wt% to 80wt% of the overall photocurable slurry.

5. The method for preparing photoluminescent transparent glass by photocuring 3D printing according to claim 1, characterized in that: In step 2, the two-step degreasing process is to first increase the temperature from room temperature to 600°C-800°C at a heating rate of 0.1°C / min-2°C / min under an argon atmosphere and keep it for two hours, cool it to room temperature, then increase the temperature from room temperature to 300°C-500°C at a heating rate of 0.1°C / min-2°C / min while introducing air, and keep it for 2 hours, and then cool it to room temperature to obtain a degreased sample.

6. The method for preparing photoluminescent transparent glass by photocuring 3D printing according to claim 1, characterized in that: In step 3, the doping modification solution is an ethanol solution prepared from one or more metal nitrates selected from cerium nitrate, strontium nitrate and aluminum nitrate, and the metal nitrate accounts for 0.1wt%-20wt% of the whole solution.

7. The method for preparing photoluminescent transparent glass by photocuring 3D printing according to claim 1, characterized in that: In step 3, the modification method is to place the decarbonized sample into a modification solution, immerse it in a vacuum solution for 1h-2h, and then place it in a drying oven at 60°C-80°C for 1-2h to obtain a modified sample.

8. The method for preparing photoluminescent transparent glass by photocuring 3D printing according to claim 1, characterized in that: In step 4, the sintering process is to place the sample in a vacuum furnace with an air pressure of 0atm-0.1atm, raise the temperature from room temperature to 1200℃-1400℃ at a heating rate of 0.5℃-2℃, keep the temperature for 2h, and then cool to room temperature to obtain photoluminescent transparent glass.

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